Dyestuffs of the naphthophenazine series



Patented May 21 1935 g a:

3 C X uniform shades. When applied to silk, the dyestufis show a very good fastness to washing and NH: water. The following examples serve to illustrate the V X IX invention, without limiting it thereto, the parts 01575 DYESTUFFS 'OF'THE NAPHTHOPHENAZINE PATENT. OFFICE.

SERIES poration o fLDelaware No Dtawirig. iApplication January 23, 1933,

7 No. 653,176. Germany February 3,

sc m (01. 260-29) l,

- Ellhe, present: :inuentiomrelates to'hew dyestuffs of :the maphthophenazine series :and to a processv of preparingisazne, :more aatticularlyit irelate's to dyestuffs :mayi ibe: represented by the probable general iormula .i

wherein .one X stands tor a. sulfonic acid group and the other Xs represent hydrogen atoms which partially may be replaced by alkyl groups and wherein the Rs stand for radicals of the benzene series. a

The new'dyes'tuffs are obtainable according to the known methods of preparing dyestufis of the azine series by reacting in the usual mannerwith an oxidizing agent upon a mixture of a 1.3- diarylaminonaphthalene-S-sulfonic acid and a monosulfonic acid of the 4.4'-diamino'-diphenylamine or its alkyl substitution products ina suitable solvent or diluent"; 7

in an alkalinesolution with sodium hypochlorite or in thepresence of acetic acid with sodium bichron ate; the preferred method of preparing my dyestuffs iconsists in "passing a current of oxygen or a, gas containing oxygen, for example air, through a weakly alkaline solution of the components in the presence-or absence of a catalyst, as for example, an ammoniacal solution of copper tetrammine. In many cases the formation of the dyestufi already takes place at room tem'- perature rather rapidly and can be accelerated by heating to 50-60 C. and/or by finely dispe'rs ing the current of air blown through the reaction mixture. f

Our new dyestuffs arenin Iorm;of their alkali metal salts generally dark powders with a bronze lustre, "soluble in water with a blue coloration, soluble in sulfuric acid with a'green tint and dyeingwool from an acidbath generally intense greenish-blue shades. 1 1

Our new dyestuffs advantageously distinguish from the known dyestuffs obtainable by condensing 4-nitroso-4'-acetamino-diphenylamino sulfonic acid with 1,3-diarylaminonaphthalene-6 or l -sulfonic acid' and saponifyingfithe acetamino group, and :mm the described in :U nited States Patent 940,354, by dyeing the the fibre more greenish shades; further they. generally yield dyeings of a-more satisfactory fastness to light, and, first of all, they, exert an excellent 7 capacity for even dyeing".

Comparediwith the safranines from 1,3-diarylaminonaphthalenefifi disulfonic acid :and 4,4-

diamino-diphenylamino "sulfonic acid, our new dyestuffs have the advantage o'f dyeing wool more 0 being by weight:

Example 1. 4 50 para 6f lL3-di-p-anisidirionaphthalene:S-sulfonic acid and 279 parts 'of l =;4'-

diaminodipheny lamino ii sul fonic acid are mixed with moo meteor 8, 50% aqueous" alcohol; then (prepared from about 20 parts of copper sulfate).

The mixture is heated to about 50]C, and at this temperature a current of air is blown through until the formation'of the dyestuii is -complete. The dyestuff is salted out withcommon salt, filtered off anddried. It is obtained as a dark crystalline'powder hayingEabron-ze lustre; is soluble in water With'a blue and in concentrated sulfuric acid with a green coloration and dyes wool from an acid bath clear greenish-{blue shades which do not change in artificial light and which have a good fastness to light/and fulling. Also the'dyeings on silk have a fastness to wash- 1 v I" The dyestuffflca'lii in fth'e' free state be represented by the probable formula =(The exact position of-the above sulfonic acidgroup is not known) .uwhenreplacing the1,3ediep-anisidinonaphthalene-S-sulfonic acid by 390 parts of 1,3-dianiish-blue shades. The dyeings on wool show a linonaphthalene-8-sulfonic acid or by 418 parts very good fastness to washing, fulling, sea water, of 1,3-di-p-toluidino-naphtalene-8-sulfonic acid, alkali and light; the dyeings on silk are fast to dyestufis exerting similar properties are obtained, washing and water. All dyeings do not change these dyestuffs having probably the following fortheir shade in artificial light.

mulae: The dyestufi may be represented by the foll l lowing probable formula sou:

nois

7 /N\ SOaH 0H3 V N- \N NH-GNH: (The exact position of this sulfonic i 0 acid group is not known) or When replacing the 4,4-diamino-3'-methyldiphenylamin-Z-sulfonic acid by the 4,4f-diamino- SOsH 3'-5-dimethyldiphenylamin-2-sulionic acid, or H1083 when using instead of the 1,3-dianilinonaphthalene-8-sulfonic acid the 1,3-di-p-t0luidinoor the 1,3-di-p-anisidino-naphthalene-8-sulfonic acid, similar dyestuffs are obtained having the probable formulas a HOaS N 7 H3 l CH3 arristers;sari N N WOW respectively, I OH l 1 When replacing the 4,4'-diaminodiphenylami- S 3 no-3-sulfonic acid by the 4,4'-diaminodiphenylamino-2-sulfonic acid a dyestufi is obtained which can be represented by the probable general formula r V g or r N- NE NH:

OOH: I

CH3 7 (The exact position of this sulfonic I acid group is not known) of Example 2.-390 parts of 1,3-dianilinonaphtha- 1ene-8-sulfonic acid and 293 parts of 4,4-diaminc-3-methyl-diphenylamine-Z-sulfonic acid are brought into a weakly alkaline reacting solution with 7000 parts of 50% aqueous alcohol and a little ammonia, andzthrough this solution a current of air is passed ata temperature of 35 to 40 C. -When the formation of the dyestufi is complete the reaction mass is heatedto 60 C., then 350 parts of commonsalt are added and the mass is stirred untiliit is cool. The dyestufi separated is filtered-oil, washed with a 50% aqueous alcohol solution being saturated with common salt and dried. A dark powder is obtained, having a bronze lustre, being soluble in water with a blue, in concentrated sulfuric acid with a greenish blue coloration, dyeing wool and silk in green- 0H5 respectively showing when dyedon wool good Iastness properties to fulling and washing.

What is claimed is: l 1. The naphthophenazine dyestuffs of the general formula whereinone X stands for a sulfonic acid group and the other Xs represent hydrogen atoms which may partially be replaced by alkyl groups, R standing for a radical of the benzene series, being in form of their alkali metal salts generally dark powders with a bronze lustre, soluble in water with a blue coloration, soluble in sulfuric acid with a green tint, dyeing wool from an acid bath generally intense greenish-blue shades.

2. The naphthophenazine dyestuffs of the general formula N -x x x R-N- NH NH:

R x x x wherein one X stands for 'a sulfonic acid group and the other Xs represent hydrogen atoms which may partially be replaced by methyl groups, R standing for a radical of the benzene series, being in form of, their alkali metal salts generally dark powders with a bronze lustre, soluble in water with a blue coloration, solubleln sulfuric acid with a green tint, dyeing wool from an acid bath generally intense greenish-blue shades. v

3. The naphthophenazine dyestuffs of the general formula wherein one X stands for a sulfonic acid group and the other Xs represent hydrogen atoms which may partially be replaced by alkyl groups,

R standing fora benzene nucleus which maybe substituted by substituents selected from the group consisting of alkyl and alkoxy, being in form of their alkali metal salts generally dark powders with a bronze lustre, soluble in water with a blue coloration, soluble in sulfuric acid with a green tint, dyeing wool from an acid bath generally intense greenish-blue shades.

4. The naphthophenazine dyestuffs of the general formula SOaH CH:

being in form of its alkali metal salts generally dark powders with a bronze lustre, soluble in water with a blue coloration, soluble in sulfuric acid with a green tint, dyeing wool from an acid bath intense greenish-blue shades.

, ELISABE'I'I-I NOCKEN, Administratria: of Theodor Nocken, Deceased.

' W'ILHLELM NEEIMEIER. 

